Supported metal nanoparticles, M-NPs, are of great scientific and economic interest as they encompass application in chemical manufacturing, oil refining and environmental catalysis. Oxidation and hydrogenation reactions are among the major reactions catalyzed by supported M-NPs. Although supported M-NPs are preferable due to their easy recovery and reuse, there are still some practical issues regarding their catalytic activity and deactivation. This review highlights the general features of supported M-NPs as catalysts with particular attention to copper, gold, platinum, palladium, ruthenium, silver, cobalt and nickel and their catalytic evaluation in various reactions. The catalytic performance of noble M-NPs has been explored extensively in various selective oxidation and hydrogenation reactions. In general, noble metals are expensive and sensitive to poisons. Despite their significant merits and potential (easily available, comparatively inexpensive and less sensitive to poisons), catalysis by base M-NPs is relatively less explored. Therefore, activity of base M-NPs can be improved, and still, there is potential for such catalysts.

Herein we report on the catalytic activity of mesoporous nickel, iron, cerium, cobalt, and manganese oxides prepared using KIT-6 as a hard template via evaporation-assisted precipitation. The mesoporous metal oxides (MMOs) were characterized and used as heterogeneous catalysts in the reduction of 4-nitrophenol (4-Nip) by sodium borohydride (BH4 –). Furthermore, polyamidoamide (PAMAM) dendrimers were used to synthesize gold–palladium nanoalloy particles. The size of AuPd/PAMAM was found to be 3.5 ± 0.8 nm in diameter before being immobilized on the aforementioned mesoporous metal oxides and used as catalysts in the reduction of 4-Nip. Prior to catalytic evaluation, the reduction profiles of the mesoporous metal oxides were investigated by hydrogen-temperature-programmed reduction (H2-TPR) and showed that mesoporous metal oxides can be easily reduced at lower temperatures and that the immobilization of gold–palladium nanoalloy particles lowers their reduction temperatures. Mesoporous cobalt and manganese oxides showed catalytic activity toward 4-Nip reduction, and the activity was enhanced after immobilization of the gold–palladium nanoalloys. Isolation of nanoparticles activity was achieved by immobilization of the gold–palladium nanoalloys on the inert silica support. From this we postulated an electron relay mechanism for the reduction of 4-nitrophenol. With the use of power rate law we showed that 4-Nip reduction follows pseudo-first-order kinetics.

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The transformation of various organic molecules into value-added chemicals has been driven by the success in development of highly active catalytic systems. Heterogeneous catalysts have found use in many industrial processes by virtue of their ease of separation and high activities in various reactions. However, many processes employing heterogeneous catalysts in the transformation of organic molecules suffer significantly when it comes to product selectivity. Herein, we report on the synthesis of highly selective palladium nanoparticle (Pd NP)-containing catalysts. The heterogeneous catalysts reported herein consist of active mixed-metal oxides, in the form of perovskites as catalysts, and as catalytic supports for Pd NPs. The activity of pure perovskites when applied as catalysts in the hydrogenation of cinnamaldehyde is 3 factors lower compared with Pd NPs immobilized on them. However, considering the fact that perovskites achieved percentage conversions between 18 and 25% in a short period of time makes them perfect candidates to replace platinum group metals in the future. In addition to being earmarked as the future of catalysis, perovskites induced a synergistic effect on the conversion of the substrate compared to when Pd NPs are immobilized on the silica support. Furthermore, these catalysts are 100% selective to hydrocinnamaldehyde and stable for up to five catalytic cycles. With regard to reusability of the catalysts, Pd/LaFeO 3 was used as a benchmark catalyst and revealed the need for surface restructuring of the catalyst for optimum activity.

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